Research Paper3D MXene anchored carbon nanotube as bifunctional and durable oxygen catalysts for Zn–air batteries
Graphical abstract
FeCo alloy nanoparticles encapsulated N-doped carbon nanotubes (CNT) have been successfully anchored on the surface of N-doped MXene.
Introduction
Developing efficient and sustainable energy conversion device is a promising strategy to tackle the current energy and climate challenge. Rechargeable Zn–air batteries (ZABs) are known as one of the candidate devices due to their high theoretical energy density and abundance of zinc metal sources [[1], [2], [3]]. However, the sluggish kinetics at the cathodes of ZABs lead to high thermodynamic overpotentials and low output power, limiting their practical applications. Expensive precious metal and its oxide are the specifically electrocatalysts currently used as cathodes materials of ZABs, thus it is demanding to improve the ZABs towards high efficiency and low cost [4].
Studies have been reported to combine transition metal nanoparticles (e.g. Co, Fe, Ni, Cu) with high conductive material (e.g. graphene nanosheet, transition metal carbides) [[5], [6], [7]], such as bimetal alloy coated in N-doped carbon nanotubes (CNTs) in suit growth with conductive material and FeP/Fe2O3 nanoparticles incorporated N, P-doped carbon aerogel [8]. However, the research into the construction of complex structures using such combinations for high-performance ZABs is rare [3].
MXenes, a new of two-dimensional (2D) transition metal carbides or nitrides exfoliated by MAX, are receiving increasing research attention in the energy conversion devices due to their essential electrochemistry properties [[9], [10], [11], [12], [13]]. For example, pristine Ti3C2Tx MXene film has been reported to exhibit attractive properties [[14], [15], [16], [17]], and MXene electrode exhibits an ultrahigh electronic transmission capability [18,19]. However, it is still far from satisfactory for its application of ZABs, because the restacking of the Ti3C2Tx layers always occur, which needs insertion processes to extend electronic transmission path [20,21]. Herein, we thought designing unique 3D MXene conductive structure could be one of the ways to deal with aggregation problem of such 2D nanosheets [[22], [23], [24], [25]].
In this work, we developed a one-pot pyrolysis method to prepare novel ZABs catalysts in 3D structure. FeCo alloy nanoparticles encapsulated N-doped carbon nanotubes (CNT) have been successfully anchored on the surface of N-doped MXene (Fe/Co-CNT@MXene-T). The resultant Fe/Co-CNT@MXene-8 catalyst exhibited outstanding electrocatalytic activities and high stability towards both ORR and OER. The bifunctional activity voltage for OER and ORR is as high as 0.73 V (vs.RHE), which surpasses precious metal benchmark Pt/C + RuO2 and most of other nonprecious metal catalysts. Fe/Co-CNT@MXene-8 also exhibited a long cyclability as a cathode in both liquid and solid ZAB systems. It could retain a remarkable stability and present a high-power density of 150 mWcm−2 during a 375 h cyclability test.
It is believed such high performances of ZABs could be explained by the following reasons: (1) The unique 3D structure consisting of 1D CNT and 2D MXene ensures the fluent charge transport; (2) The bamboo-like CNT with large surface area not only can exposes more active sites, but also speed up the electrolytes streaming and oxygen molecules flow; (3) The N dopant onto the metal surface improves surface defects and potential energy; (4) The synergistic effect of active sites FeCo nanoparticles improves the catalytic activity.
Section snippets
Materials
All the materials were used without any additional purification. Polyethyleneimine (PEI, MW = 600), cobalt nitrate hexahydrate (Co(NO3)2.6H2O), melamine, ferric chloride hexahydrate (FeCl3⸱6H2O), zinc acetate (Zn(CH3COO)2), MAX (Ti3AlC2), lithium fluoride (LiF), hydrochloric acid (HCl, 37.5 wt%), potassium hydroxide (KOH), Commercial Pt/C (Pt, 20 wt%) and RuO2. Nafion solution (5 wt%). The deionized water (18.25 MΩ)” was replaced by “All the materials were used without any additional
Results and discussion
The preparation of Fe/Co-CNT@MXene-T catalyst is schematically illustrated in Fig. 1. The MXene (Ti3C2Tx) nanosheets were first produced by delaminating MAX (Ti3AlC2) with HCl/LiF under ultrasonic treatment [[26], [27], [28]](Fig. 2a). MAX phase has a micron-size block structure (Fig. S1a). The XRD shift at the peak of 10° to a smaller angle and the greatly weakened peak at 39° support the formation of MXene (Fig. S1b). The AFM results show that the prepared MXene are multilayer, with an
Conclusions
A 3D-structured bifunctional ORR/OER catalyst, CoFe nanoalloy decorated CNT anchoring with 2D MXene, has been successfully synthesized. The ZAB equipped with our Fe-Co/CNT@MXene-8 cathode exhibited a high energy and power density, stable voltage output, and remarkable stability in both aqueous and solid system. One reason for such high performance and stability can be contributed to the 3D structure. The CNT reorganize the alignment of the Ti3C2 flakes, making the electronic transport pathways
CRediT authorship contribution statement
Chao Zhang: Conceptualization, Methodology. Huifeng Dong: Data curation. Binling Chen: Writing – review & editing. Tianxu Jin: Data curation. Jun Nie: Supervision. Guiping Ma: Supervision, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgment
This work was supported by the National Natural Science Foundation of China (Grant No. 51973009). The project was funded by State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Dong Hua University. (KF2105)
References (57)
- et al.
Auto-programmed heteroarchitecturing: self-assembling ordered mesoporous carbon between two-dimensional Ti3C2Tx MXene layers
Nano Energy
(2019) - et al.
MXene based self-assembled cathode and antifouling separator for high-rate and dendrite-inhibited Li–S battery
Nano Energy
(2019) - et al.
Ti3C2Tx MXene core-shell spheres for ultrahigh removal of mercuric ions
Chem. Eng. J.
(2019) - et al.
Functionalized chitosan electrospun nanofiber membranes for heavy-metal removal
Polymer
(2019) - et al.
Harnessing the interplay of Fe–Ni atom pairs embedded in nitrogen-doped carbon for bifunctional oxygen electrocatalysis
Nano Energy
(2020) - et al.
Surface/interface nanoengineering for rechargeable Zn–air batteries
Energy Environ. Sci.
(2020) - et al.
A rechargeable zinc-air battery based on zinc peroxide chemistry
Science
(2021) - et al.
A high-rate and long-life organic-oxygen battery
Nat. Mater.
(2019) - et al.
Recent advances in carbon-based bifunctional oxygen catalysts for zinc-air batteries
Batteries Supercaps
(2019) - et al.
Bifunctional N-CoSe2/3D-MXene as highly efficient and durable cathode for rechargeable Zn–air battery
ACS Mater. Lett.
(2019)
Aggregation-resistant 3D MXene-based architecture as efficient bifunctional electrocatalyst for overall water splitting
ACS Nano
Integrated and binder-free air cathodes of Co3Fe7 nanoalloy and Co5.47N encapsulated in nitrogen-doped carbon foam with superior oxygen reduction activity in flexible aluminum-air batteries
Adv. Sci.
An iron-decorated carbon aerogel for rechargeable flow and flexible Zn-air batteries
Adv. Mater.
Self-assemble and in situ formation of Ni1−x FexPS3 nanomosaic-decorated MXene hybrids for overall water splitting
Adv. Energy Mater.
In situ grown MWCNTs/MXenes nanocomposites on carbon cloth for high-performance flexible supercapacitors
Adv. Funct. Mater.
Strain engineering of a MXene/CNT hierarchical porous hollow microsphere electrocatalyst for a high-efficiency lithium polysulfide conversion process
Angew Chem. Int. Ed. Engl.
Two-dimensional molybdenum carbide (MXene) as an efficient electrocatalyst for hydrogen evolution
ACS Energy Lett.
MXene-bonded activated carbon as a flexible electrode for high-performance supercapacitors
ACS Energy Lett.
Fast gelation of Ti3C2Tx MXene initiated by metal ions
Adv. Mater.
Hydrophobic, flexible, and lightweight MXene foams for high-performance electromagnetic-interference shielding
Adv. Mater.
Electrochemical actuators based on two-dimensional Ti3C2Tx (MXene)
Nano Lett.
Trifunctional single-atomic Ru sites enable efficient overall water splitting and oxygen reduction in acidic media
Small
A polymer-direct-intercalation strategy for MoS2/carbon-derived heteroaerogels with ultrahigh pseudocapacitance
Nat. Commun.
Maximizing ion accessibility in MXene-knotted carbon nanotube composite electrodes for high-rate electrochemical energy storage
Nat. Commun.
Alkylammonium cation intercalation into Ti3C2 (MXene) effects on properties and ion-exchange capacity estimation
Chem. Mater.
2D MXene nanofilms with tunable gas transport channels
Adv. Funct. Mater.
Two-dimensional titanium carbide (MXene)-wrapped sisal-Like NiCo2S4 as positive electrode for High-performance hybrid pouch-type asymmetric supercapacitor
Chem. Eng. J.
Guidelines for synthesis and processing of two-dimensional titanium carbide (Ti3C2Tx MXene)
Chem. Mater.
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